Violet sulfur dye and process of making same.



UNITED STATES Patented January 10, 1905.

PATENT OFFICE.

ARTHUR LUTTRINGHAUS, OF LUDVVIGSHAFEN-ON-THE-RHINE, GERMANY,

ASSIGNOR TO 'BADISOHE ANILIN & SODA FABRIK, OF LUDVVIGSHAFEN- ON-THE-RHINE, GERMANY, A CORPORATION OF BADEN.

VIOLET SULFUR DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 779,860, dated January10, 1905.

Application filed December 22, 1903- Serial No. 186,196.

To all whom it may concern:

Be it known that I, ARTHUR LUTTRINGHAUS,

a subject of the King of Prussia, Emperor of Germany, residing atLudwigshafen-on-the Rhine, in the Kingdom of Bavaria, Empire of Germany,have invented new and useful Improvements in Sulfur Ooloring- Mattersand Processes of Obtaining the Same, of which the followingis aspecification.

I have discovered that if equimolecular proportions ofortho-ortho-dichlor-para-phenylene-diamin and a phenol be oxidizedtogether the reaction proceeds smoothly and there are obtained largequantities of new indophenols which are stable and which when treatedwith sulfur and alkali sulfid give rise to new sulfurized dyestuffswhich have great coloring power and great affinity for cotton. The saidnew indophenols can be very easily reduced,

and the resulting diphenylamin derivatives can be used instead of thecorresponding indophenols in the preparation of the said new sulfurizeddyestuffs.

Asa matter of convenience I give an example of a method for preparingthe intermediate indophenolic body which is used inthe preparation ofone of my new sulfur dyestuffs. The parts are by weight.

Emmple 1Prepm'at0a 0 f indophenol 0 from ort/w ortho (Zia/blow 1mmphenylaladamn in and p/Lm0Z.Seventyfive (75) parts of orthoortho-dichlor para phenylene diamin are dissolved in thirty five hundred(3,500) parts of water and three hundred and 3 5 twenty (320) parts ofhydrochloric acid, containing about thirty per cent. of H01. To this isadded a solution of forty-two (42) parts of phenol in one thousand(1,000) parts of water, and the whole is cooled to zero centigrade, 4o(0C. ,)and two thousand(2,000) parts ofice are added. Thisis stirred,and while stirring a so lution of eighty (80) parts of bichromate infour hundred L00) parts of water is added all at once. After the furtheraddition of a solu- 45 tion of one hundred and nine (109) parts ofcrystallized sodium acetate in four hundred (400) parts of water theindophenol is filtered oh and well washed and pressed and dried.

The new indophenol is a fairly-stable body. For instance, it is onlygradually decomposed 5 after long standing with thirty (30) per cent.acetic acid. It is very easily reduced-for example, by an aqueoussolution of sodium sulfidto the corresponding diphenylamin which isobtained from its solutions in colorless crystals and dissolves readilyin caustic-soda solution, yielding a colorless solution which in the airrapidly turns reddish blue, while the indophenol is graduallyprecipitated.

Instead of phenol in the above reaction other phenols, such asorthocresol or meta-.. cresol, can be employed.

The following example will serve to further illustrate themethod bywhich my new dyestutfs may be obtained; but I do not confine 5 myinvention to this example. The parts are by weight.

Ewample 2-Pwpamti0n 0 f the sulfum'zed' dyestufia-Eighty parts of theindophe nol prepared according to example 1 from 7 ortho-ortho-dichlorpara phenylene diamin and phenol are introduced into a solution of twohundred and forty (240) parts of crystal.- lized sodium sulfid in twohundred and forty (240) parts of water. Forty (40) parts of sul- 75 furare then added and the brown'solution is evaporated in a vessel providedwith a stirring apparatus till its temperature has risen to one hundredand twenty degrees centigrade, (120 O.) The vessel is then closed andfitted with 30 a reflux condenser, and the contents of the vessel areheated until the indophenol has almost or entirely disappeared. Thegreenish-brown mass is then taken up with thirty-fivehundred (8,500)parts of boiling water, and the solu- 5,

tion is filtered, and air is passed through the filtrate, whereupon thedyestutf separates out as adark powder and is filtered off and pressedand dried.

The dyestutf is practically insoluble in the 9 usual organic solvents.It dissolves in concentrated sulfuric acid, the solution being blue.

It dissolves in a small quantity of sodium sulfid, the solution beingviolet. In excess of sodium sulfid, however, similarly to the relatedindophenols it very easily undergoes reduction to the leuco compound.These sodium-sulfid solutions dye unmordanted cotton greenish-gray tobluish-gray shades, which on exposure to the air rapidly turn deepviolet. A dyestuflof similar properties is obtained if in the aboveexample instead of the indophenol the corresponding diphenylamin besubstituted and also if either the indophenol or the diphenylamin beheated with alkali polysulfid to a higher temperature-for example, aboutone hundred and sixty degrees centigrade, (160 (1) In these cases theraw melt can be used directly for dyeing, or the dyestuf'f can beseparated by dissolving the melt in water and passing air through thesolution.

The same procedure is followed for. the production of sulfurizeddyestuffs from the other indophenols obtained according to example 1.

